CN1058504C - Aqueous polymer dispersion used for varnish - Google Patents
Aqueous polymer dispersion used for varnish Download PDFInfo
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- CN1058504C CN1058504C CN93112648A CN93112648A CN1058504C CN 1058504 C CN1058504 C CN 1058504C CN 93112648 A CN93112648 A CN 93112648A CN 93112648 A CN93112648 A CN 93112648A CN 1058504 C CN1058504 C CN 1058504C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
Abstract
An aqueous polymer dispersion based on polyester and acrylate is obtained by radical polymerisation of at least (a) one (meth)acrylic acid ester and (b) one ethylenically unsaturated, at least monofunctional acid and if required (c) one ethylenically unsaturated monomer different from (a) and (b), or mixtures thereof, with a radically polymerisable polyester resin. Also disclosed is a process for producing said aqueous polymer dispersions, aqueous transparent lacquers containing these aqueous polymer dispersions and their use.
Description
The present invention relates to the aqueous polymer dispersion based on polyester based and acrylate-based graftomer, its preparation method contains the moisture varnish of this dispersion liquid, with and uses thereof.
Usually, people labour for the composition that reduces organic solvent in the varnish, in the paint technology field, and automotive paints particularly, but also comprise in other field, exist keen interest to containing the sealing wax system.
Under the situation that body of a motor car paints in batch, after so-called " priming paint/varnish " operation, preferably be coated with multilayer paint.In addition, will go up colored primer earlier, after of short duration air seasoning, not carry out japanning with varnish under the baking.And then priming paint and varnish are toasted together.This method will produce the very paint of high value on optics and the technology.
According to prior art as can be known, priming paint belongs to Aquo System, and in automobile industry, and this priming paint is by coming into operation in batch sometimes.What usually also wish these people is the superiors, and promptly varnish can be developed suitable Aquo System and corresponding use.
For this reason, so characteristic this contains the water meter lacquer and must be equal to mutually with the varnish of routine in being dissolved in organic solution at least.Solid content by spraying concentration must be very high, utilizes one or two jet pipe just can reach sufficiently high coat-thickness to cause.Meanwhile, after baking, this paint film must have good distribution and very high smooth finish.In addition, this film should be transparent and " plentiful ", and has good " state ".
It is important also that in addition this film is repairable.Finish on the first layer paint of baking, do not having under the polishing, must repair with all priming paint commonly used as much as possible, this paint be good adhesion and be anti-pure stone, in addition, this paint must have favorable durability with respect to chemical erosion, for example anti-fuel, acid (sulfuric acid) or alkali.In addition, it is important that this paint is sweat proof water.
DE-Os3128062 has described can be by vinylbenzene, (methyl one) acrylate, vinyl ester, the monomer of hydroxyl, (methyl one) vinylformic acid, possible acrylamide and/or Methacrylamide and the moisture decomposer of the multipolymer by affixture preparation that branched monocarboxylic glycidyl ester and unsaturated carboxylic acid polymerization are obtained in the presence of anionic emulsifier, combine with aminoplast(ic) resin, produced heat-setting coating thus.For according to the Application Example 3 that provides in this patent and 4 and in conjunction with for the two-layer paint of conventional metal-priming paint production weather, this emulsion polymer should be enough.Yet, in conjunction with moisture priming paint 40 ℃ permanent chamber atmosphere surpass 240 hours (DIN50017) but after toolability and sweat proof water-based do not provide.
EP-A-365775, DE-OS3834738, DE-OS4009931 and DE-OS4009932 have described solution polymer, and this solution polymer prepares by this way, be exactly not carboxylic monomer and carboxylic monomer in organic solvent mutually or the part alternative carry out radical polymerization.The weathering resistance of the varnish film that makes thus, particularly anti-sulfuric acid and caustic soda are far from being enough.
Described the aqueous coating agent that contains as the polyester oligomer-polyacrylic ester of main component in EP-A-0391271, said polyester oligomer-polyacrylic ester makes by the radical polymerization at ethylenically unsaturated monomer hydroxyl-functional, in can not the polyester oligomer of radical polymerization.The anti-sulfuric acid of the varnish film that makes thus is very poor.
DE-OS4027594 has described the moisture varnish that contains as the emulsion polymer of binding agent, and this polymkeric substance uses at the same time under special fluorizated, the ethylenically unsaturated monomer and makes.
DE-OS4010176 has described and has contained the moisture priming paint that is bonded to dispersion, this dispersion makes by this way, in the presence of the urethane resin that contains polymerizable double bond, in organic solvent, ethylenically unsaturated monomer is carried out radical polymerization, and the reaction product that will so obtain changes into aqueous dispersion.The application DE-OS4010176 that is produced moisture varnish by this adhesive dispersions does not address.
Therefore, task of the present invention provides a kind of aqueous polymer dispersion, and this dispersion is enough to be used for aqueous paint as the binding agent component.
According to the present invention, this task will be solved with acrylate-based aqueous polymer dispersion by polyester based; This dispersion is that the radical polymerization by following component obtains; The following at least composition of 20-80% (weight):
(a) (methyl one) acrylate of monohydroxy-alcohol or polyvalent alcohol can also contain free hydroxyl group at this this ester.
(b) olefinic undersaturated, be the acid of simple function at least, with dispensable (c), olefinic is undersaturated, (a) and the different monomer of (b) or their mixture, but vibrin with the radical polymerization of 80～20% weight, its per molecule has 0.2～1.5 polymerizable two strands, and molecular weight is from 300～5000, its can by the polyvalent alcohol of divalence at least and at least divalence the poly carboxylic acid or derivatives thereof the polyvalent alcohol that contains a polymerizable two strands at least and/or polycarboxylic in the presence of carry out polycondensation and make; In the case, with quantitative (a) and (b), (c) and vibrin input, make the polymkeric substance that obtains have the acid number of 30～200 hydroxyl values and 5～100.
(methyl one) acrylate as unit alcohol or polyvalent alcohol, when this ester can also contain free hydroxyl group, the ester of methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, the trimethyl carbinol, isopropylcarbinol, vinyl carbinol, hexalin, ethylhexyl alcohol, lauryl alcohol or the stearyl alcohol of this ester will be used; When this ester is the ester of polyvalent alcohol, the ethylene glycol, 1 of this monoesters or diester, 2-or 1, ammediol, 1,4-butyleneglycol or 1, the ester of 6-hexylene glycol will be used.
Acid undersaturated as olefinic, simple function at least (b) can be used vinylformic acid, methacrylic acid, vinyl sulfonic acid, butenoic acid, toxilic acid, half fat of fumaric acid, methylene-succinic acid or toxilic acid, fumaric acid or methylene-succinic acid.
Different monomer (c) undersaturated as olefinic, (a) and (b) can use vinylbenzene, alpha-methyl styrene, Vinyl toluene, acrylamide, methacryloyl, vinyl cyanide or methacrylonitrile; Monomer (c) also may be with the form of monomer mixture.
The method that the preparation of vibrin can be used always according to those of skill in the art, with dicarboxylic acid or its suitable derivative, for example possible acid anhydrides carries out esterification with glycol and realizes.For example in the presence of esterifying catalyst commonly used, solution temperature is carrying out as under 180～230 ℃ the rising temperature in this esterification.
In addition, can make spent glycol as the polyvalent alcohol of divalence at least, 1,3-and 1, the 2-propylene glycol, 1,4-butyleneglycol, 1, the 5-pentanediol, 1,6-hexylene glycol, 2,2-dimethyl propylene glycol, glycol ether, triglycol, Tetraglycol 99, hexaethylene glycol, 1,3-hydroxymethyl-cyclohexane, 1,4-hydroxymethyl-cyclohexane, glycerine, TriMethylolPropane(TMP) or tetramethylolmethane.
For the poly carboxylic acid of the divalence at least for preparing polyester, can use Succinic Acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid, phthalic acid, m-phthalic acid, terephthalic acid, tetrahydrobenzene dioctyl phthalate, bridged ring tetrahydrobenzene dioctyl phthalate in the hexahydrobenzene dioctyl phthalate, methylene, 1,2-, 1,3-or 1,4-cyclohexane diacid, muconic acid and dextrocamphoric acid, trimellitic acid, tricarballylic acid, dimethylol propionic acid or their acid anhydrides.
In order in this polyester molecule, to introduce polymerisable double bonds, should use simultaneously contain polymerizable double bond polyvalent alcohol and/or poly carboxylic acid.
At least the example that contains the polyvalent alcohol of a polymerizable double bond is an allylin, trishydroxymethyl mono allyl ether, butylene glycol or dihydroxymethyl propylene mono allyl ether.
At least the polycarboxylic example that contains a polymerizable double bond is a toxilic acid, fumaric acid, and methylene-succinic acid or glycidyl allyl ether or epihydric alcohol methylpropenoic acid ester are to containing the adduct of carboxy(l)polyester.
Equally also possible is, at first prepares carboxylic polyester, then, this hydroxyl and the monomer with Oxyranyle such as glycidyl allyl ether or epihydric alcohol methylpropenoic acid ester is carried out addition.
Particularly, each molecule of this vibrin contains 0.5～1.0 polymerizable with key.Similarly, this vibrin from 500～2000 molecular weight also is preferred.
Particularly, this aqueous polymer dispersion demonstrates 50～150 hydroxyl value.For this aqueous dispersion, acid number is preferably 15 to 40.
Another task according to the present invention provides the preparation method of aqueous polymer dispersion.
This task can solve by this way according to the present invention, at first, with the miscible wholly or in part organic solution of water in, but the vibrin that adds the radical polymerization of 80% to 20% weight, its per molecule has 0.2～1.5 polymerisable double bonds, molecular weight is from 300～50000, it is by the polyvalent alcohol of divalence at least and the poly carboxylic acid or derivatives thereof of divalence at least, the polyvalent alcohol that contains a polymerizable double bond at least and/or polycarboxylic in the presence of condensation reaction obtain, add the vibrin of 20～80% weight of following at least composition then:
(a) (methyl one) acrylate of unit alcohol or polyvalent alcohol, wherein this ester also can contain free hydroxyl group;
(b) olefinic undersaturated, be acid and dispensable (c) of simple function at least; Olefinic is undersaturated, different monomers or its mixture of (a) and (b); Carry out polymerization then in the presence of free-radical initiator, product that will so obtain and alkali neutralization again is scattered in the water, and under dispensable decompression, steams and reserve organic solvent.
As organic solvent, be used particularly with water can be miscible wholly or in part more such organic solvents.At this particularly suitable solvent is ethanol, propyl alcohol, butanols, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), butyleneglycol, ethylene glycol, propylene glycol, N-Methyl pyrrolidone, ethylene glycol dimethyl ether, methoxybutanol or diacetone alcohol.
As the suitable compound of free-radical initiator as ditertiary butyl peroxide, two cumenyl superoxide, dibenzoyl peroxide, dilauroyl peroxide, cumene inclusion of hydroperoxide, tertiary butyl inclusion of hydroperoxide, t-butylperoxyl benzoate is crossed the pivalic tert-butyl ester, mistake-3,5, the 5-tri-methyl hexanoic acid tert-butyl ester, the mistake-2 ethyl hexanoic acid tert-butyl ester, two-2-ethylhexyl-peroxide, two carbonic ethers, dicyclohexyl one peroxide two carbonic ethers, 1,1-two (t-butyl peroxy)-3,5,5-trimethyl-cyclohexane, 1,1-two (t-butyl peroxy), cyclohexanone peroxide, peroxidation methyl butyl ketone, 2,2 '-azo-two (2,2,2 the 4-methyl pentane nitrile), '-azo-two (2-methylbutyronitrile), 1,1 '-azo-two-cyclohexanenitrile or azo-two-isopropyl cyanide.
Radical polymerization itself will carry out between 80 and 160 ℃ temperature.
Should so select the amount of the monomer (a) and (b) and possible (c) of hydroxyl,, preferred 50～150 with the hydroxyl value that causes the whole aqueous dispersion relevant from 30～200 with solid, especially preferably from 80 to 120.
For the stability of aqueous polymer dispersion, this is very important, and the polymkeric substance that makes according to the present invention contains enough can form anionic group, preferred carboxyl.Be not only the polyester composition, and be that (methyl one) vinylformic acid composition can both be introduced into this polymkeric substance; But they can also be introduced in two steps, yet the present invention is (methyl one) acrylate composition (a) preferably.The acid number of the polymkeric substance that makes according to the present invention can be between 5 and 100, preferably between 15 and 40.
Just use multiple unsaturated monomer (a), (b) or dispensable (c), exist the such danger of gelling.Therefore, must adjust such monomeric kind and the such condition of quantity.If necessary, it may be suitable using so-called rule jointly.Such rule description is in EP-A-158161.Therefore, the present invention relates to as lauryl mercaptan or dredge compound so the basic ethanol.
After polymerization was finished, what will carry out was to change into aqueous dispersion.Must will be able to the anionic group of form to small part neutralize in advance for this reason.In this case, be neutralized to PH7～10, preferred 7.3～8.5.
For neutralization, the mixture that can use alkali such as ammonia or volatile primary, second month in a season and/or uncle's organic amine, particularly ethamine, dimethylamine, triethylamine, morpholine, croak pyridine, diethanolamine, trolamine, dimethylethanolamine or obtain thus.Yet, particularly preferably be the dimethyl diethanolamine, it is useful adding as the neutralizing agent that contains water diluent.
After in being scattered in water, can under reduced pressure organic solvent be evaporated whole or in part if desired.
The solids content of the dispersion that obtains thus is between 30 and 55% weight, preferably between 35 and 50% weight.The polymer dispersion liquid that so obtains can be used to prepare aqueous paint, especially for successive, two-layer lacquer, especially for the aqueous paint of body of a motor car.
Therefore, the present invention relates to aqueous coating agent in addition, particularly moisture varnish, this varnish contains polyester based and acrylate-based aqueous polymer dispersion and the water-soluble and/or emulsible linking agent of water, thus, the ratio of dispersion solid constituent and linking agent is between 60: 40 and 85: 15.
As linking agent, if it is water-soluble or can becomes water miscible by adding organic solvent that so, when it was used to paint the field, each common amino resin crosslinking agent all was suitable for.This is water-soluble or will be according to currently known methods by adding the water-soluble aminoresin of organic solvent, by aldehyde particularly the compound of formaldehyde and band polyamino or many imido grpups (for example trimeric cyanamide, urea element, Dyhard RU 100 and benzocarbamidine or this class mixture of products) reaction and make.The preferred Melmex that uses.
Also can replace aminoresin to mix the emulsible polymeric polyisocyanate of water as linking agent for this aqueous polymer dispersion, and handle as two component varnish, and in self-vulcanizing.(end capped) polymeric polyisocyanate that also can use the water soluble camouflage is as linking agent.
According to aqueous coating agent of the present invention, external except polymer dispersed of the present invention, also can comprise other water-soluble binding agent, as polyester, polyethers, polyurethane, polyacrylic ester and aminoplast(ic) resin.
According to varnish of the present invention, except that a small amount of organic solvent, also can comprise blend commonly used.Thus, the content of organic solvent is between 5 and 20% weight, preferably below 15% weight.Particularly preferred solvent is 1,2-propylene glycol and butyl Diethylene Glycol.
As blend commonly used, suitable example has levelling agent, carminative, dispersing auxiliary, anti-photic aging agent, anti-sludging agent, or glidant.
Varnish of the present invention can be coated with by utilisation technology commonly used.Coating technique has spraying, preferably with the electrostatic spraying of high speed rotating cover.But, also can pass through hairbrush, scraper plate or dipping are coated with.
Varnish of the present invention can be coated with coat-thickness commonly used.
Moisture varnish of the present invention is particularly suitable for the varnish external coating (EC) as multilayer paint in the automotive industry.Compare with the system that contains organic solvent of routine, the characteristics of varnish of the present invention are to have a spot of solvent, and high solids content and low viscosity are arranged.Depend on the organic solvent that uses low levels, the characteristics of moisture varnish of the present invention also are to be suitable for environment.
Moisture varnish of the present invention can be coated with on moisture or water-free priming paint " wet to wet ".Wet and do not use varnish the surface drying of preceding priming paint to foreclose wet application; Solidify, more precisely bake process (for example 130～160 ℃, 15～30 minutes) is carried out simultaneously.
The characteristics of the paint film that is made by moisture varnish system according to the present invention are to contain with known that solvent system is the same to have a good equally degree of performance.These performances such as surface hardness, transparency, glossiness, fillibility (Fiille), flowability, scratch soundness, elasticity, anti-dissolubility agent, anti-toolability, anti-certain chemical is as anti-sulfuric acid, alkali resistance, anti-buffering fluidity, anti-diesel oil and petrol-resistance, anti-short period of time and wind erosion property for a long time, at least with the same good by the performance that contains the Aquo System gained paint film of knowing in solvent system or other prior art known, however under normal conditions will be better.
Be not only aqueous polymer dispersion, and be that the moisture varnish that makes has thus all demonstrated good preservation stability.
Following example is used for explaining the present invention.
Embodiment:
Polyester A
Fusing is 92 part 1 in the 2L reactor of agitator and packed column is housed, the 6-hexylene glycol, 73 parts of TriMethylolPropane(TMP) mono allyl ethers, 250 parts of neopentyl glycol, 80 parts of TriMethylolPropane(TMP)s, 554 parts of hexanaphthenes-1,2-dicarboxylic anhydride and 2 parts of dibutyltin oxides, and under agitation heat, make column top temperature be no more than 100 ℃.Therefore, the temperature of reaction mixture should be greater than 230 ℃.Esterification time is for reaching acid number less than till 4 o'clock.After being cooled to, with 328 parts of methyl ethyl ketones reactant is diluted to 75% solid content less than 80 ℃.
So obtain theoretical molecular-weight average is 1680, and hydroxyl value is the polyester of 100 (at solid resins).
Polyester B
Use 92 part 1,6-hexylene glycol, 55 parts of allylins, 250 parts of neopentyl glycol, 80 parts of TriMethylolPropane(TMP)s, 554 parts of hexanaphthenes-1,2-dicarboxylic anhydride and 2 parts of dibutyltin oxides.
As this polyester of the described preparation of polyester A.
Regulate solid contents to 75% with methylethylketone after the esterification.
So obtain theoretical molecular-weight average is 1570, and hydroxyl value is the polyester of 107 (at solid resins).
Polyester C
Use 92 part 1,6-hexylene glycol, 48 parts of glycidyl allyl ethers, 250 parts of neopentyl glycol, 80 parts of TriMethylolPropane(TMP)s, 554 parts of hexanaphthenes-1,2-dicarboxylic anhydride and 2 parts of dibutyltin oxides.
As this polyester of the described preparation of polyester A.After esterification, use methyl ethyl ketone, solids content is adjusted to 75%.So obtain theoretical molecular-weight average is 1570, and hydroxyl value is the polyester of 107 (at because of the body resin).
Polyester D
Use 92 part 1,6-hexylene glycol, 209 parts of TriMethylolPropane(TMP) mono allyl ethers, 169 parts of neopentyl glycol, 80 parts-hydroxymethyl-propane, 554 parts of hexanaphthenes-1,2-dicarboxylic anhydride and 2 parts of dibutyltin oxides.
As this polyester of the described preparation of polyester A.After esterification, use methyl ethyl ketone, solid content is adjusted to 75%.So obtain theoretical molecular-weight average is 1680, and hydroxyl value is the polyester of 100 (at solid resins).
Polyester E
Use 142 part 1,6-hexylene glycol, 250 parts of neopentyl glycol, 80 parts of TriMethylolPropane(TMP)s, 508 parts of hexanes-1 not, 2-dicarboxylic anhydride, 29 parts of maleic anhydrides, 2 parts of dibutyltin oxides and 0.15 part of Jonol CP.
As this polyester of the described preparation of polyester A, after esterification, use methyl ethyl ketone, solid content is transferred to 75%.So obtain theoretical molecular-weight average is 1570, and hydroxyl value is the polyester of 107 (at solid resins).
Polyester F
Use 92 part 1,6-hexylene glycol, 37 parts of butylene glycol-2,250 part neopentyl glycol, 80 parts-hydroxymethyl-propane, 554 parts of not hexane-1,2-dicarboxylic anhydride and 2 parts of dibutyltin oxides.
As this polyester of the described preparation of polyester A.After esterification, use methyl ethyl ketone, solid content is transferred to 75%.So obtain theoretical molecular-weight average is 1530, and hydroxyl value is the polyester of 110 (at solid resins).
Embodiment 1
Agitator, thermometer are being housed, are adding 532 parts of vibrin A and 76 parts of methyl ethyl ketones in the 4L reactor of reflux exchanger and two feeders.
Add by 103 parts of butyl methacrylate 20 parts of single vinylbenzene (Mono-Styrol), 48 parts of vinylformic acid 2-hydroxypropyl esters, 53 parts of methacrylic acid 2-hydroxypropyl esters and 17 parts of monomer mixtures that vinylformic acid is formed therein in a feeder.In another feeder, get ready by 10 part 2,2 '-initiator solutions that azo-two-isopropyl cyanide (AIBN) and 69 parts of methyl ethyl ketones are formed.After reactor content was heated to 80 ℃, in 3 hours, polymerization starter solution added in the reactor in 3.5 hours simultaneously with monomer mixture.Polymerization temperature maintains 80 ℃.This injection was carried out 1.5 hours at 80 ℃ after finishing again.Then, add 13 parts of dimethylethanolamines (corresponding degree of neutralization is 60%) and 1000 parts of softening waters.The highest 55 ℃, methyl ethyl ketone is fallen in underpressure distillation.So obtain solid content is 43%, and the pH value is 7.70 dispersion.The acid number of this polymkeric substance is 18, and hydroxyl value is 111.
Embodiment 2
Agitator is being housed, is adding 532 parts of polyester B and 76 parts of methyl ethyl ketones in the 4L reactor of reflux exchanger and two feeders.In addition all handle by embodiment 1.After removing methyl ethyl ketone, obtaining solid content is 40%, and pH value is 7.5 dispersion.
Embodiment 3
Agitator is being housed, is adding 532 parts of polyester C and 76 parts of methyl ethyl ketones in the 4L reactor of reflux exchanger and two feeders.In addition, all handle by embodiment 1.After removing methyl ethyl ketone, obtain solid content and be 38%, pH value is 7.65 dispersion.
Embodiment 4
In the 4L reactor that agitator, reflux exchanger and two feeders are housed, add 532 parts of polyester D and 76 parts of methyl ethyl ketones.In monomer mixture, add additional 14 parts and dredge basic ethanol.In addition, all handle by embodiment 1.After removing methyl ethyl ketone, obtain solid content and be 39%, pH value is 7.70 dispersion.
Embodiment 5
Agitator is being housed, is adding 532 parts of polyester E and 76 parts of methyl ethyl ketones in the 4L reactor of reflux exchanger and two feeders.In addition, all handle, after removing methyl ethyl ketone, obtain solid content and be 46%, pH value is 7.30 dispersion by embodiment 1.
Embodiment 6
Agitator is being housed, is adding 532 parts of polyester F and 76 parts of methyl ethyl ketones in the 4L reactor of reflux exchanger and two feeders.In addition, all handle by embodiment 1.After removing methyl ethyl ketone, obtain solid content and be 42%, pH value is 7.40 dispersion.
Embodiment 7
Agitator is being housed, is adding 532 parts of polyester A and 76 parts of methyl ethyl ketones in the 4L reactor of reflux exchanger and two feeders.Monomer mixture is by 84 parts of butyl methacrylate, 84 parts of tert-butyl acrylates, and 20 parts of single vinylbenzene, 38 parts of 2-ethylhexyl acrylates, 48 parts of vinylformic acid 2-hydroxypropyl esters, 53 parts of methacrylic acid 2-hydroxypropyl esters and 17 parts of vinylformic acid are formed.In addition, all handle by embodiment 1.After removing methyl ethyl ketone, obtain solid content and be 41%, pH value is 7.90 dispersion.
Embodiment 8
Agitator is being housed, is adding 532 parts of polyester A and 76 parts of methyl ethyl ketones in the 4L reactor of reflux exchanger and two feeders.Monomer mixture is by 84 parts of butyl methacrylate, 84 parts of tert-butyl acrylates, and 20 parts of single vinylbenzene, 38 parts of stearyl acrylate base esters, 48 parts of vinylformic acid 2-hydroxypropyl esters, 53 parts of methacrylic acid 2-hydroxypropyl esters and 17 parts of vinylformic acid are formed.In addition, all handle by embodiment 1.After removing methyl ethyl ketone, obtain solid content and be 38%, pH value is 7.90 dispersion.
Embodiment 9
In the 4L reactor that agitator, thermometer, reflux exchanger and two feeders are housed, add 532 parts of vibrin A and 76 parts of methyl ethyl ketones.
Add by 103 parts of butyl methacrylate 103 parts of tert-butyl acrylates, 20 parts of single vinylbenzene, 48 parts of vinylformic acid 2-hydroxypropyl esters and 53 parts of monomer mixtures that methacrylic acid 2-hydroxypropyl ester is formed therein in a feeder.In another feeder, get ready by 3 part 2,2 '-initiator solutions that azo-two-isopropyl cyanide (AIBN) and 69 parts of methyl ethyl ketones are formed.After reactor content is heated to 80 ℃, monomer mixture was added reactor in 1 hour 45 minutes.After adding, immediately 25 parts of vinylformic acid were added in 15 minutes.Polymerization starter solution added in 2.5 hours simultaneously.Polymerization temperature maintains 80 ℃.After feeding finishes, also need to stir 1.5 hours at 80 ℃.Add 27 parts of dimethylethanolamines (corresponding degree of neutralization is 80%) and 1000 parts of softening waters then.The highest 55 ℃, methyl ethyl ketone is fallen in underpressure distillation, so obtain that solid content is 42%, pH value is 7.70 dispersion.The acid number of this polymkeric substance is that 27 hydroxyl values are 111.
Embodiment 10
In the 4L reactor that agitator, thermometer, reflux exchanger and two feeders are housed, add 532 parts of vibrin A and 76 parts of methyl ethyl ketones.
Add by 75 parts of butyl methacrylate 75 parts of tert-butyl acrylates, 74 parts of single vinylbenzene, 48 parts of vinylformic acid 2-hydroxypropyl esters and 53 parts of monomer mixtures that methacrylic acid 2-hydroxypropyl ester is formed therein in a feeder.In another feeder, get ready by 10 part 2,2 '-initiator solutions that azo-bis-isobutyronitrile (AIBN) and 69 parts of methyl ethyl ketones are formed.After reactor content is heated to 80 ℃, monomer mixture was added in the reactor in 2 hours 40 minutes.After adding end, and then in 20 minutes, 25 parts of vinylformic acid are added.Simultaneously, polymerization starter solution added in 3.5 hours.Polymerization temperature maintains 80 ℃.After feeding finishes, also will stir 1.5 hours.Then, add 33 parts of dimethylethanolamines (corresponding degree of neutralization is 100%) and 1000 parts of softening waters.Methyl ethyl ketone is fallen in underpressure distillation under the highest 55 ℃ temperature.So obtain solid content and be 42%, pH value is 8.50 dispersion, the acid number of polymkeric substance is 27, hydroxyl value 111.
Comparative Examples
Polyester G (Comparative Examples of EP-A-391271)
Use 92 part 1,6-hexylene glycol, 293 parts of neopentyl glycol, 80 parts of TriMethylolPropane(TMP)s, 554 parts of hexanaphthenes-1,2-dicarboxylic anhydride and 2 parts of oxygen dibutyl tins.This polyester of preparation described in polyester A.After the esterification, utilize methyl ethyl ketone that solid content is transferred to 80%.So obtain theoretical molecular-weight average and be 1590, hydroxyl value is the polyester of 106 (at solid resins).
Polyester H (simultaneous test of EP-A-391271)
Use 354 part 1,6-hexylene glycol, 402 parts of TriMethylolPropane(TMP)s and 438 parts of hexanodioic acids.This polyester of preparation described in polyester A.So obtain theoretical molecular-weight average and be 362, hydroxyl value is 405 polyester.
Polyester I (simultaneous test of DE-OS4010176)
Use 366 part 1,6-hexylene glycol, 323 parts of neopentyl glycol and 679 parts of hexanodioic acids.This polyester of preparation described in polyester is so obtain that theoretical molecular-weight average is 362, hydroxyl value is 145 polyester.
Embodiment 11
In the 4L reactor that agitator, reflux exchanger and two feeders are housed, add 499 parts of polyester G and 109 parts of methyl ethyl ketones.Handle as embodiment 1.In order to be scattered in the water, use 23 parts of dimethylethanolamines (corresponding 100% degree of neutralization) and 1400 parts of softening waters.After removing methyl ethyl ketone, obtain unsettled dispersion.After the short period of time, this dispersion precipitation is very severe.
Embodiment 12
In the 4L reactor that agitator, reflux exchanger and two feeders are housed, add 499 parts of polyester G and 109 parts of methyl ethyl ketones, monomer mixture is by 95 parts of butyl methacrylate, 95 parts of tert-butyl acrylates, 20 parts of single vinylbenzene, 48 parts of vinylformic acid 2-hydroxypropyl esters, 53 parts of methacrylic acid 2-hydroxypropyl esters and 34 parts of vinylformic acid are formed.In order to be scattered in the water, use 42 parts of dimethylethanolamines (corresponding 100% degree of neutralization) and 1400 parts of softening waters.In addition, all handle as embodiment 1.After removing methyl ethyl ketone, obtain unsettled dispersion.After the short period of time, this dispersion precipitation is very severe.
Embodiment 13 (simultaneous test of EP-A-391271)
In the 2L reactor of agitator, reflux exchanger and feeder is housed, add 359 parts of polyester H and 156 parts of butyleneglycols, and be heated to 140 ℃.In 4 hours, in this container, add by 276 parts of single-butanediol acrylates 473 parts of tert-butyl acrylates, 37 parts of vinylformic acid and 50 parts of mixtures that t-butylperoxyl benzoate is formed, and post polymerization 4 hours.
Embodiment 14 (simultaneous test of EP-A-365775)
In the 2L reactor that agitator, thermometer, reflux exchanger and two feeders are housed, add 200 parts of butyleneglycols, and be heated to 140 ℃.
Add by 200 parts of butyl methacrylate 220 parts of vinylformic acid butyric acid, 150 parts of single vinylbenzene, 150 parts of methacrylic acid methyl and 230 parts of monomer mixtures that vinylformic acid 2-hydroxypropyl ester is formed therein in a feeder.In another feeder, get ready by 45 parts of t-butylperoxyl benzoates and 50 parts of initiator solutions that butyleneglycol is formed.After reactor content is heated to 140 ℃, in 3 hours 50 minutes, monomer mixture is added.After interpolation finishes, and then 50 parts of vinylformic acid were added in 20 minutes.Meanwhile, polymerization starter solution was added in 3.5 hours.Polymerization temperature maintains 140 ℃, after feeding finishes, also should stir 2.5 hours at 140 ℃, after the cooling, adds 49 parts of dimethylethanolamines (corresponding 80% degree of neutralization) and 383 parts of deionized waters.So obtain solid content and be 60% dispersion.
Embodiment 15 (simultaneous test of DE-OS-4010176)
In being housed, the 6L reactor of agitator, thermometer and reflux exchanger adds 343 parts of polyester I, 29 parts of neopentyl glycol, 18 parts of TriMethylolPropane(TMP) mono allyl ethers, 258 parts of methylethylketones, 259 parts of isophorone diisocyanates, with 0.4 part of dibutyl tin laurate, and then under nitrogen atmosphere, be heated to 80 ℃.At NCO content is 55 parts of TriMethylolPropane(TMP)s of adding in 2% o'clock.Allow be reflected at 80 ℃ and proceed, till NCO content O%.Add 253 parts of methyl ethyl ketones then.
Add by 232 parts of methyl methacrylates 232 parts of butyl acrylates, 285 parts of methacrylic acid 2--hydroxypropyl esters and 36 parts of monomer mixtures that vinylformic acid is formed therein in a feeder.In another feeder, get ready by 24 part 2,2 '-initiator solutions that azo-bis-isobutyronitrile (AIBN) and 158 parts of methyl ethyl ketones are formed.Monomer mixture is added in 3 hours at 80 ℃.Polymerization starter solution added in 3.5 hours simultaneously.Polymerization temperature maintains 80 ℃.After feeding finishes, also should stir 2.5 hours in 80 ℃.Add 36 parts of dimethylethanolamines (corresponding 80% degree of neutralization) and 1750 parts of softening waters then.Under reduced pressure distill out methyl ethyl ketone.So obtain solid content and be 41%, pH value is 7.40 dispersion.The acid number of polymkeric substance is 18, and hydroxyl value is 100.Application Example 1～10 (application of preparation embodiment 1～10):
Under stirring fast, with the adhesive dispersions of 266 parts of (at solid resin) embodiment 1～10 respectively with 90% solution of 127 parts of commercial terpolycyantoamino-formaldehyde resins general, water-dilutable (Cymel327R) and 95 parts, 1,2-propylene glycol thorough mixing.Then, utilize dimethylethanolamine that every part pH value is transferred to 8.60～8.70.And then in every part, add one by one by 0.09 part of commercial general levelling agent (Fluorad FC 430
R) and 0.81 part of butyleneglycol and the 4.6 parts of commercial general additive that contains silicone resin (Additol XW 329
R) mixture formed and mixing.Utilize softening water that every part viscosity is transferred to 27 seconds (pressing the DIN4mm cup in 20 ℃ measures).
Application Example 11 (application of the Comparative Examples 13 of corresponding EP-A-391271);
Under stirring fast, (Cymel 327 with the dispersion of 250 parts of embodiment 13 and 148 parts of commercial terpolycyantoamino-formaldehyde resins general, water-dilutable
R) solution and 36 parts of butyleneglycol thorough mixing of 90%.Then, pH value is transferred to 8.60 to 8.70, regulate viscosity with softening water with dimethylethanolamine.
Application Example 12 (application of the Comparative Examples 14 of corresponding EP-A-365775);
Under stirring fast, (Cymel 327 with the trimeric cyanamide-formaldehyde resin of the commercial general water-dilutable of the dispersion of 400 parts of examples 14 and 66 parts
R) 90% solution and commercial general levelling agent (Fluorad FC 430
R) thorough mixing.With dimethylethanolamine pH value is transferred to 8.60～8.70 then.And then regulate viscosity with softening water.
Application Example 13 (application of Comparative Examples 15):
Under high-speed stirring, (Cymel 327 with the trimeric cyanamide-formaldehyde resin of the commercial general water-dilutable of the dispersion of 500 parts of examples 15 and 99 parts
R) 90% solution and 25 part 1,2-propylene glycol thorough mixing transfers to 8.60～8.70 with dimethylethanolamine with pH value then.And then add by 0.07 part of commercial general levelling agent (Fluorad FC 430
R) and 0.63 part of butyleneglycol and the 1.4 parts of commercial general additive that contains silicone resin (Additol XW 329
R) and 25 parts of mixtures that Dowanol DPnB forms, and mix.With softening water viscosity is transferred to 27 seconds (pressing DIN 4mm cup in 20 ℃ measures).
The varnish that obtains is sprayed the thickness of 35～40 μ m on pre-metal one priming paint prior to 10 minutes water-dilutable of 100 ℃ of dryings; In 80 ℃ predrying 10 minutes, then in 150 ℃ the baking 20 minutes.The coating (seeing Table 1) that test obtains:
Table 1
Contrast test Application Example 123456789 10 11 12 13 atomizing viscosities, (second) 27 27 27 27 27 27 27 27 27 27 35 24 27 solid contents, (%) 40 41 40 40 40 4l, 41 37 37 44 51 41 35 adhesion GT, 0 GT, 0 GT, 0 GT, 0 GT, 0 GT, 0 GT, 0 GT, 0 GT, 0 GT, 0 GT l GT, 0 GT, 0 sweat test++++++++++-++ anti-dimethylbenzene++ +++++++ ++ ++ +++--++ anti-H2SO
4++++++++ +++++---Nai NaOH ++ ++ ++ ++ ++ ++ ++ ++ ++ ++ ++--++ Knoop hardness 14.8 15.8 15.3 12.7 18.9 14.8 15.2 15.8 14.9 23.7 15.8 3.6 15.8 cuppings (mm) 5.0 8.4 9.9 9.1 8.5 8.7 7.1 6.5 6.7 7.0 7.4 10.2 6.4
[++]=fine.[+]=good, [-]=poor, [--]=very poor
Claims (27)
1. based on polyester based and acrylate-based aqueous polymer dispersion, it is characterized in that this dispersion is that the radical polymerization by following material obtains the following at least material of 80-20% weight:
(a) (methyl) acrylate of monohydroxy-alcohol or polyvalent alcohol, wherein, this ester also contains free hydroxyl group,
(b) acid of the undersaturated simple function at least of olefinic and dispensable (c): olefinic is undersaturated, be different from (a) and monomer (b) or their mixture; But vibrin with the radical polymerization of 20-80% weight, its per molecule has 0.2-1.5 polymerizable double bond, and molecular weight is 300-5000, its can by the how pure and mild binary at least of binary poly carboxylic acid or derivatives thereof at least the polyvalent alcohol that contains a polymerizable double bond at least and/or polycarboxylic in the presence of carry out polycondensation and make, in the case, with quantitative (a) and (b), (c) and vibrin input, make the polymkeric substance that obtains have the hydroxyl value of 30-200 and the acid number of 5-100.
2. aqueous polymer dispersion as claimed in claim 1, it is characterized in that, as (methyl) acrylate of unit alcohol, use the ester of methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, the trimethyl carbinol, isopropylcarbinol, vinyl carbinol, hexalin, ethylhexyl alcohol, lauryl alcohol or stearyl alcohol; As the ester of polyvalent alcohol, make spent glycol, 1,2-or 1, ammediol, 1,4-butyleneglycol or 1, the monoesters of 6-hexylene glycol or diester.
3. as the aqueous polymer dispersion of claim 1 or 2, it is characterized in that undersaturated as olefinic, vinylformic acid is used in the acid of simple function at least, methacrylic acid, vinyl sulfonic acid, butenoic acid, toxilic acid, fumaric acid, methylene-succinic acid, or the half ester of use toxilic acid, fumaric acid or methylene-succinic acid.
4. aqueous polymer dispersion as claimed in claim 1 is characterized in that,, (a) and (b) different monomers undersaturated as olefinic, use vinylbenzene, alpha-methyl styrene, Vinyl toluene, acrylamide, Methacrylamide, vinyl cyanide or methacrylonitrile.
5. aqueous polymer dispersion as claimed in claim 1 is characterized in that, as how pure binary is at least, makes spent glycol, 1,3-and 1,2-propylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 2,2-dimethyl propylene glycol, glycol ether, triglycol, Tetraglycol 99, hexaethylene glycol, 1,3-hydroxymethyl-cyclohexane, or 1,4-hydroxymethyl-cyclohexane, glycerine, TriMethylolPropane(TMP) or tetramethylolmethane.
6. aqueous polymer dispersion as claimed in claim 1 is characterized in that, as binary poly carboxylic acid at least, uses Succinic Acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid, phthalic acid, m-phthalic acid, terephthalic acid, tetrahydrobenzene dioctyl phthalate, bridged ring tetrahydrobenzene dioctyl phthalate in the hexahydrobenzene dioctyl phthalate, methylene, 1,2-, 1,3-or 1,4-cyclohexane diacid, muconic acid and dextrocamphoric acid, trimellitic acid, tricarballylic acid, dimethylol propionic acid or their acid anhydrides.
7. aqueous polymer dispersion as claimed in claim 1 is characterized in that, as the polyvalent alcohol that contains a polymerizable double bond at least, uses allylin, TriMethylolPropane(TMP) mono allyl ether, 1,4-butyleneglycol or dimethylol propionic acid mono allyl ether.
8. aqueous polymer dispersion as claimed in claim 1, it is characterized in that,, use toxilic acid as the poly carboxylic acid that contains a polymerizable double bond at least, fumaric acid, methylene-succinic acid or glycidyl allyl ether or epihydric alcohol methylpropenoic acid ester are to containing the adduct of carboxy(l)polyester.
9. aqueous polymer dispersion as claimed in claim 1 is characterized in that, this vibrin per molecule contains 0.5-1.0 polymerisable double bonds.
10. aqueous polymer dispersion as claimed in claim 1 is characterized in that this dispersion has the hydroxyl value of 50-150.
11. the aqueous polymer dispersion as claim 10 is characterized in that, this dispersion has the hydroxyl value of 80-120.
12. aqueous polymer dispersion as claimed in claim 1 is characterized in that, this dispersion acid number is 15-40.
13. the preparation method of aqueous polymer dispersion as claimed in claim 1, it is characterized in that, with water wholly or in part in the blended organic solvent, but the vibrin that adds the radical polymerization of 20-80% weight, per molecule has 0.2-1.5 polymerisable double bonds, molecular weight is 300-5000, and it is by the how pure and mild binary at least of binary poly carboxylic acid or derivatives thereof at least, the polyvalent alcohol that contains a polymerizable double bond at least and/or polycarboxylic in the presence of condensation reaction obtain; The vibrin that contains following at least component that adds 80-20% weight then;
(a) (methyl) acrylate of unit alcohol or polyvalent alcohol, wherein, this ester contains free hydroxyl group,
(b) undersaturated, the acid of simple function at least of olefinic, with dispensable (c): olefinic is undersaturated, be different from (a) and monomer (b) or its mixture, in the presence of free-radical initiator, carry out polymerization then, product that will so obtain and alkali neutralization again, be scattered in the water, and under dispensable decompression, distill out organic solvent.
14. the method as claim 13 is characterized in that, as organic solvent, use ethanol, propyl alcohol, butanols, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), butyleneglycol, ethylene glycol, propylene glycol, N-Methyl pyrrolidone, ethylene glycol dimethyl ether, methoxybutanol or diacetone alcohol.
15. the method as claim 13 is characterized in that, as free-radical initiator, use ditertiary butyl peroxide, two cumenyl superoxide, dibenzoyl peroxide, dilauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, t-butylperoxyl benzoate is crossed the pivalic tert-butyl ester, mistake-3,5, the 5-tri-methyl hexanoic acid tert-butyl ester, cross-the 2 ethyl hexanoic acid tert-butyl ester, two-2-ethylhexyl-peroxide, two carbonic ethers, dicyclohexyl-peroxide two carbonic ethers, 1,1-two (t-butyl peroxy)-3,5, the 5-trimethyl-cyclohexane, 1,1-two (t-butyl peroxy) hexanaphthene, cyclohexanone peroxide, the peroxidation methyl iso-butyl ketone (MIBK), 2,2 ' azo-two (2, the 4-methyl pentane nitrile), 2,2 '-azo-two (2-methylbutyronitrile), 1,1 '-azo-two-cyclohexanenitrile or azo-two-isopropyl cyanide.
16. the method as claim 13 is characterized in that, uses ammonia or volatile primary, second month in a season and/or uncle's organic amine as alkali.
17. the method as claim 16 is characterized in that, described organic amine is an ethamine, dimethylamine, triethylamine, morpholine, piperidines, diethanolamine, trolamine, dimethylethanolamine or the mixture that obtains thus.
18. the method as claim 13 is characterized in that, polymerization is that the temperature between 80 and 160 ℃ is carried out.
19. the method as claim 13 is characterized in that, is neutralized to pH7-10.
20. the method as claim 19 is characterized in that, is neutralized to pH7.5-9.
21. an aqueous polymer dispersion, this dispersion contain according among the claim 1-10 any one aqueous dispersion and with it blended as the aminoresin and the universal paint additive of linking agent.
22. the aqueous polymer dispersion as claim 21 is characterized in that, as aminoresin, uses water-soluble and/or the dispersible aminoresin of water.
23. the aqueous polymer dispersion as claim 22 is characterized in that, described aminoresin is by aldehyde and is with the reaction of the compound of polyamino or many imido grpups to make.
24. the aqueous polymer dispersion as claim 22 is characterized in that, uses melamine formaldehyde resin as aminoresin.
25. the aqueous polymer dispersion as claim 21 is characterized in that, makes the emulsible polymeric polyisocyanate of water substitute aminoresin as linking agent.
26. the aqueous polymer dispersion as claim 21 is characterized in that, this coating-forming agent exists with the form of varnish.
27. the aqueous polymer dispersion as claim 21 is characterized in that, this coating-forming agent contains as 1 of solvent, the 2-propylene glycol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4242518.2 | 1992-12-16 | ||
| DE4242518A DE4242518C2 (en) | 1992-12-16 | 1992-12-16 | Aqueous polymer dispersions for clear coats |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1090293A CN1090293A (en) | 1994-08-03 |
| CN1058504C true CN1058504C (en) | 2000-11-15 |
Family
ID=6475470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93112648A Expired - Fee Related CN1058504C (en) | 1992-12-16 | 1993-12-16 | Aqueous polymer dispersion used for varnish |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5648410A (en) |
| EP (1) | EP0674672B2 (en) |
| CN (1) | CN1058504C (en) |
| AT (1) | ATE155500T1 (en) |
| AU (1) | AU5810394A (en) |
| DE (2) | DE4242518C2 (en) |
| ES (1) | ES2107802T5 (en) |
| TW (1) | TW242635B (en) |
| WO (1) | WO1994013720A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4419216C1 (en) * | 1994-06-01 | 1995-08-31 | Bollig & Kemper | Aq. clearcoat compsn. for multilayer paint systems |
| WO1999042533A1 (en) | 1998-02-18 | 1999-08-26 | Ppg Industries Ohio, Inc. | Low temperature cure waterborne coating compositions having improved appearance and humidity resistance and methods for coating substrates |
| GB9807213D0 (en) | 1998-04-04 | 1998-06-03 | Ici Ltd | Aqueous coating composition |
| US6270905B1 (en) | 1999-02-16 | 2001-08-07 | Ppg Industries Ohio, Inc. | Multi-component composite coating composition and coated substrate |
| DE19957161A1 (en) * | 1999-11-27 | 2001-06-13 | Basf Coatings Ag | Aqueous dispersions of acrylate-modified alkyd resins and their use |
| RU2255101C2 (en) | 2000-05-19 | 2005-06-27 | Акцо Нобель Н.В. | Aqueous cross-linking binding composition and composition for covering, lacquer sealing agent composition comprising such binding composition |
| JP2002302639A (en) * | 2001-04-06 | 2002-10-18 | Kansai Paint Co Ltd | Aqueous coating composition for inner surface of can |
| DE10234794A1 (en) * | 2002-07-31 | 2004-04-08 | Basf Coatings Ag | Basecoats containing fatty acid-modified epoxy esters and / or fatty acid-modified alkyd resins, process for their preparation and their use |
| DE10237576A1 (en) * | 2002-08-16 | 2004-02-26 | Bayer Ag | Aqueous binder dispersions as coating agents |
| US20040132895A1 (en) * | 2002-08-30 | 2004-07-08 | Ambrose Ronald R. | Compositions and methods for coating food cans |
| DE10261006A1 (en) * | 2002-12-24 | 2004-07-08 | Degussa Ag | Dispersions of amorphous, unsaturated polyester resins based on certain dicidol isomers |
| DE10261005A1 (en) * | 2002-12-24 | 2004-07-08 | Degussa Ag | Dispersions of amorphous, urethanized unsaturated polyester resins based on certain dicidol isomers |
| CN1946819A (en) * | 2004-02-12 | 2007-04-11 | 瓦尔斯帕供应公司 | Methods of coating interior container surfaces and containers containing internal coatings |
| ITMI20060670A1 (en) * | 2006-04-05 | 2007-10-06 | Ivm S R L | PAINT RESIN BASED ON POLYESTER RESINS STYRENE-FREE POLINSATURE |
| US7649634B2 (en) | 2007-10-30 | 2010-01-19 | Mountain View Optical Consultant Corp. | Methods and systems for white light interferometry and characterization of films |
| CN101367899B (en) * | 2008-10-17 | 2010-09-08 | 广东同步化工股份有限公司 | Preparation method for silver drop-proof thermoplastic acrylic resin |
| JP5826079B2 (en) * | 2012-03-16 | 2015-12-02 | 日本ペイント・オートモーティブコーティングス株式会社 | Jet black multilayer coating film and method for forming the same |
| US20130295293A1 (en) * | 2012-05-07 | 2013-11-07 | Super-Flex, Llc | Coating composition for creating protective layer over solid surfaces |
| CN102766238B (en) * | 2012-08-13 | 2013-10-30 | 佛山市高明同德化工有限公司 | High-adhesion thermoset acrylic resin and preparation method thereof |
| EP3810669A1 (en) * | 2018-06-20 | 2021-04-28 | PPG Industries Ohio Inc. | An acrylic polyester resin and an aqueous coating composition containing the same |
| WO2021144210A1 (en) * | 2020-01-16 | 2021-07-22 | Basf Coatings Gmbh | Coating composition comprising a poly(ethylene-acrylate) copolymer and method of coating substrates |
| CN114560979A (en) * | 2020-11-27 | 2022-05-31 | 万华化学集团股份有限公司 | Modified polyester/acrylate resin hybrid aqueous dispersion, preparation method thereof, varnish and colored paint for baking paint |
| CN114231116A (en) * | 2021-12-29 | 2022-03-25 | 上海昱邦化工科技有限公司 | Water-based high-gloss high-wear-resistance varnish and preparation method thereof |
| EP4273176A1 (en) * | 2022-05-06 | 2023-11-08 | Röhm GmbH | Production of alkyl(meth)acrylate polyester copolymers by means of suspension polymerization |
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1993
- 1993-12-13 TW TW082110539A patent/TW242635B/zh active
- 1993-12-14 EP EP94903771A patent/EP0674672B2/en not_active Expired - Lifetime
- 1993-12-14 AT AT94903771T patent/ATE155500T1/en active
- 1993-12-14 AU AU58103/94A patent/AU5810394A/en not_active Abandoned
- 1993-12-14 US US08/448,399 patent/US5648410A/en not_active Expired - Lifetime
- 1993-12-14 WO PCT/EP1993/003530 patent/WO1994013720A1/en active IP Right Grant
- 1993-12-14 DE DE59306944T patent/DE59306944D1/en not_active Expired - Lifetime
- 1993-12-14 ES ES94903771T patent/ES2107802T5/en not_active Expired - Lifetime
- 1993-12-16 CN CN93112648A patent/CN1058504C/en not_active Expired - Fee Related
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| US4259224A (en) * | 1976-10-02 | 1981-03-31 | Hoechst Aktiengesellschaft | Copolymer solution of acrylic resin, process for its manufacture and use thereof in reactive lacquers |
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Also Published As
| Publication number | Publication date |
|---|---|
| ATE155500T1 (en) | 1997-08-15 |
| US5648410A (en) | 1997-07-15 |
| AU5810394A (en) | 1994-07-04 |
| EP0674672B2 (en) | 2003-11-26 |
| DE4242518C2 (en) | 1996-10-02 |
| TW242635B (en) | 1995-03-11 |
| EP0674672A1 (en) | 1995-10-04 |
| DE59306944D1 (en) | 1997-08-21 |
| WO1994013720A1 (en) | 1994-06-23 |
| ES2107802T5 (en) | 2004-07-01 |
| DE4242518A1 (en) | 1994-06-23 |
| EP0674672B1 (en) | 1997-07-16 |
| CN1090293A (en) | 1994-08-03 |
| ES2107802T3 (en) | 1997-12-01 |
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